高等学校化学学报 ›› 2025, Vol. 46 ›› Issue (10): 20250202.doi: 10.7503/cjcu20250202

• 有机化学 • 上一篇    下一篇

可见光催化烯烃的硅酰基化反应

姬宝宝, 王智香, 刘艳, 曹佳()   

  1. 延安大学化学与化工学院,陕西省化学反应工程重点实验室,延安 716000
  • 收稿日期:2025-07-19 出版日期:2025-10-10 发布日期:2025-08-29
  • 通讯作者: 曹佳 E-mail:jcao@yau.edu.cn
  • 基金资助:
    国家自然科学基金(22162024);国家自然科学基金(22272144);陕西高校青年创新团队项目(24JP207);教育部产学研合作育人项目(2412064200);教育部产学研合作育人项目(2412063658)

Visible-light Photocatalytic Silylacylation of Alkenes

JI Baobao, WANG Zhixiang, LIU Yan, CAO Jia()   

  1. Shaanxi Key Laboratory of Chemical Reaction Engineering,College of Chemistry and Chemical Engineering,Yan’an University,Yan’an 716000,China
  • Received:2025-07-19 Online:2025-10-10 Published:2025-08-29
  • Contact: CAO Jia E-mail:jcao@yau.edu.cn
  • Supported by:
    the National Natural Science Foundation of China(22162024);the Research Project of Youth Innovation Team of Shaanxi Universities, China(24JP207);the Collaborative Education Project of the Ministry of Education, China(2412064200)

摘要:

硅硼化物作为硅自由基前体在有机合成中备受关注, 已成为研究热点. 本文发展了在可见光催化下实现硅硼化物和酰基氮盐对烯烃的三组分双官能化反应, 合成了一系列高附加值含硅的酮化物. 通过机理实验和理论计算研究发现, 光催化下碱/硅基硼酸酯络合物与酰基氮盐进行单电子转移, 继而产生的硅基自由基和酰基盐自由基阴离子依次与烯烃偶联, 最终生成在β位有硅烷基的酮类化合物. 该方法具有良好的官能团耐受性、 温和的反应条件和广泛的底物适用范围.

关键词: 光催化, 烯烃, 硅, 酰基

Abstract:

Carbonyl compounds are prevalent in bioactive molecules and organic functional materials, with ketones being particularly important structural motifs. This work focuses on the development of a visible-light photocatalytic three-component difunctionalization of alkenes using silylborates and acyl ammonium salts to access ketone derivatives. Control experiments and DFT calculations revealed that reaction proceeds via a single-electron transfer cascade process between a base/silylboronate complex and an acyl ammonium salt, triggered by a photocatalyst, generating silyl radicals and acyl radical anions. Subsequent sequential coupling with alkenes affords β-silyl ketones. This method features excellent functional group tolerance, mild reaction conditions, and broad substrate scope.

Key words: Photocatalysis, Alkene, Silylation, Acylation

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